3-exo-tet Cyclization of 2,2-disubstituted 1,3-dihalopropanes with indium in aqueous and ionic liquid solvent system

Article abstract of DOI:10.1016/j.tet.2009.06.123

The 3-exo-tet cyclization of 2,2-disubstituted 1,3-dihalopropanes with In powder in THF solution of 20% H₂O, dioxane solution of 20% H₂O, and ionic liquids, such as [bmim]Br, [bmim]Cl, and [bmin]BF₄, respectively, was effi

Full text of DOI:10.1016/j.tet.2009.06.123

Tetrahedron 65 (2009) 7533–7537
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
3-exo-tet Cyclization of 2,2-disubstituted 1,3-dihalopropanes with indium
in aqueous and ionic liquid solvent system
*
Yuhsuke Tsuchiya, Yuhta Izumisawa, Hideo Togo
Graduate School of Science, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 27 May 2009
Received in revised form 29 June 2009
Accepted 29 June 2009
Available online 3 July 2009
The 3-exo-tet cyclization of 2,2-disubstituted 1,3-dihalopropanes with In powder in THF solution of 20%
H2O, dioxane solution of 20% H2O, and ionic liquids, such as [bmim]Br, [bmim]Cl, and [bmin]BF4, re-
spectively, was efficiently carried out to form the corresponding 1,1-disubstituted cyclopropanes in good
yields. The cyclopropanation of 2,2-disubstituted 1,3-dihalopropanes with In powder in ionic liquids,
such as [bmim]Br, [bmim]Cl, and [bmin]BF4, was markedly accelerated compared with that in a THF
solution of 20% H2O and a dioxane solution of 20% H2O. The mechanism was proposed to involve the
radical 3-exo-tet cyclization of the formed 3-halopropyl radical.
Keywords:
3-exo-tet
1,3-Dihalopropane
Cyclopropane
Indium
Ó 2009 Elsevier Ltd. All rights reserved.
Ionic liquid
Cyclization
1. Introduction
ring strain7 and the carbon-centered radicals are generally nucleo-
philic; therefore, electron-deficient olefinic groups are required.8
Highly strained cyclopropane structures are known to exist in
a wide variety of naturally occurring products which are in some
cases, potent biological activity.1 For example, hormosirene and
dictyopterene, which are seaweed pheromones, are hydrocarbons
containing cyclopropane and olefinic groups.1b Therefore, the syn-
thetic study of the cyclopropane ring is very important. The most
useful and practical methods for the formation of cyclopropanes
with olefinic groups have been well carried out with free carbene
derived from haloform under basic conditions,2 diazo-olefins with
the Rh catalyst,3 the Simmons–Smith reactions,4 and others.5 These
cyclopropanation reactions proceed effectively, especially in the
case of diazo-olefins with the Rh catalyst and the Simmons–Smith
reaction. However, generally, electron-rich olefins are required as
these reactions proceed via an electrophilic manner. On the other
hand, the preparation of cyclopropanes via radical pathway is very
attractive and challenging. There are three types for the radical
formation of cyclopropanes, i.e., radical 3-exo-trig cyclization, radi-
cal 3-exo-tet cyclization, and radical 3-exo-dig cyclization, based on
Baldwin’s rule,6 although the study is rather limited. A few reports of
cyclopropanation in the radical 3-exo-trig manner are known.
However, for radical 3-exo-trig cyclization, the formed cyclo-
propylmethyl radicals are thermodynamically unstable because of
Initially, when methyl 5-bromo-4,4-dimethoxy-2-pentenoate was
treated with Bu3SnH and AIBN in refluxing benzene, the expected
cyclopropane derivative was not formed9 because the ring-opening
reaction of the formed cyclopropylmethyl radical occurred rapidly.
On the other hand, electrochemical reductive cyclization of ethyl 5-
methanesulfonyloxy-4,4-dimethyl-2-pentenoate was effectively
carried out to form the corresponding cyclopropane.10 Photolysis of
2-substituted butyrophenones gave the corresponding cyclopropyl
phenyl ketones through a Norrish II type pathway.11 As regards
metal-induced radical 3-exo-trig cyclization, the formation of 11
hydroxy-5,9-cyclopregnane-3,20-dione by single electron transfer
(SET) reduction of 9 -bromo-11 -hydroxyprogesterone bearing a
-bromo- -unsaturated ketone group, with chromous acetate was
reported.12 Treatment of
-iodo- and -bromo- -unsaturated es-
ters with SmI2 in the presence of tert-butyl alcohol in THF gave the
corresponding cyclopropanes.13 The same treatment of
-di-
substituted -oxo- -unsaturated esters with SmI2 in the presence
b-
a
b
d
a,b
d
d
a,b
g,g
d
a,b
of tert-butyl alcohol in THF provided the corresponding cyclo-
propanols via ketyl radicals.14 To the best of our knowledge, studies
of the radical 3-exo-tet cyclization of 1,3-dihalopropanes are ex-
tremely limited. Thus, 1,3-dihalides, mainly 1,3-diiodopropane de-
rivatives, could be reductively cyclized to cyclopropanes by metal
reduction with Na,15a–c halogen–metal exchange using t-BuLi,16 and
use of a metal hydride, such as LiAlH4.15b,c It is proposed that some of
these reactions proceed through a radical pathway. Treatmentof 1,3-
diiodopropanewith benzoyl peroxide at110 ꢀCgavecyclopropanein
* Corresponding author.
E-mail address: togo@faculty.chiba-u.jp (H. Togo).
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.06.123

7534
Y. Tsuchiya et al. / Tetrahedron 65 (2009) 7533–7537
quite good yield.17 Treatment of 2,2-disubstituted 1,3-diiodopro-
pane with Bu3SnH in refluxing benzene gave the corresponding
cyclopropane in good yield.15c As a related reaction, the formation of
cyclopropanes from the reaction of 2-substituted 1,3-diiodopro-
panes with (C6F13CH2CH2)3SnH or Ph3SnH and AIBN under highly
diluted conditions through the homolytic cyclization of the in-
termediate 3-iodoalkyl radicals, radical 3-exo-tet manner, was
reported, and the radical cyclization proceeds in the range of
Dioxane, a mixture of THF and water, and a mixture of dioxane and
water worked as good reaction solvents. However, THF alone did not
work efficiently (entry 1). Based on these results, 2,2-di(aryl-
methyl)-1,3-diiodopropanes bearing p-methylphenyl, p-methoxy-
phenyl, and p-chlorophenyl groups were treated with In powder to
give the corresponding 1,1-di(arylmethyl)cyclopropanes in good
yields (entries 5–16), especially in THF solution of 20% H2O and
dioxane solution of 20% H2O. The reactivity of 2,2-dialkyl and 2,2-
dialkenyl substituted 1,3-diiodopropanes was also sufficient in
refluxing THF solution of 20% H2O and dioxane solution of 20% H2O,
although THF alone did not work well again (entries 17–24).
Then, 2,2-di(arylmethyl)-1,3-dibromopropanes were treated
with In powder (2.4 equiv) for 24 h in the same solvents under
refluxing conditions. However, the reaction did not proceed effi-
ciently in spite of use of an excess amount of In powder, and the
starting material was recovered. Therefore, the reaction was car-
ried out for 48 h under refluxing conditions in THF, dioxane, THF
solution of 20% H2O, and dioxane solution of 20% H2O to provide
the corresponding 1,1-di(arylmethyl)cyclopropanes, as shown in
Table 2. Again, dioxane solution of 20% H2O and THF solution of
20% H2O under refluxing conditions showed good reactivity to
provide the corresponding cyclopropanes in good yields (entries
1–16). The same treatment of 2,2-dialkyl and 2,2-alkenyl 1,3-
dibromopropanes with In powder in THF solution of 20% H2O and
dioxane solution of 20% H2O gave the corresponding cyclopro-
panes in good yields.
5ꢁ105 s
.
ꢂ118 These results suggest that radical 3-exo-tet cyclization
may proceed effectively according to Baldwin’s rule where 3-exo-tet
cyclization is favored.6 Recently, we reported a simple and efficient
method for the preparation of disubstituted and monosubstituted
cyclopropanes from corresponding 1,3-dihalopropanes. The first
one involved the reaction of 1,3-dihalopropanes with Zn powder in
refluxing ethanol.19 However, the yields of cyclopropanes when 1,3-
dibromopropanes were used, were low, while 1,3-dichloropropanes
did not react at all under the same conditions. The second one in-
volved the reaction of 1,3-dihalopropanes with SmI2 in refluxing
THF.20 However, SmI2 is extremely air-sensitive and is therefore not
easy to handle.
Here, as part of our study toward environmentally benign or-
ganic syntheses using radical reactions,21 we would like to report
a simple yet efficient In-mediated 3-exo-tet cyclization of 2,2-di-
substituted 1,3-dihalopropanes to provide the corresponding cy-
clopropanes in good yields in a THF solution of 20% H2O, a dioxane
solution of 20% H2O, and ionic liquids, such as [bmim]Br, [bmim]Cl,
and [bmin]BF4.
Table 2
Preparation of cyclopropanes from 1,3-dibromopropanes with In powder
2. Results and discussion
R
R
Br
Br
R
R
In (2.4 eq.)
When 2,2-dibenzyl-1,3-diiodopropane was treated with In
powder (2.4 equiv), which is known as one of the SET reagents,22 for
24 h in THF, dioxane, THF solution of 20% H2O, dioxane solution of
20% H2O, 1,1-dibenzylcyclopropane was obtained in 9%, 93%, 100%,
and 97% yields, respectively, as shown in Table 1 (entries 1–4).
Solvent, reflux, 48 h
Entry
R–
Solvent
Yielda (%)
1
THF
10 (79)b
33 (60)b
76
2
Dioxane
3
THF of 20% H2O
4
5
6
7
8
9
Dioxane of 20% H2O
THF
Dioxane
THF of 20% H2O
Dioxane of 20% H2O
THF
81
10 (74)b
10 (71)b
87
Table 1
Preparation of cyclopropanes from 1,3-diiodopropanes with In powder
CH3
R
R
I
I
R
R
In (2.4 eq.)
Solvent, reflux, 24 h
92
10 (85)b
89
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
Dioxane
CH3O
Cl
THF of 20% H2O
Dioxane of 20% H2O
THF
16 (74)b
89
Entry
R–
Solvent
Yielda (%)
30 (55)b
85
1
2
THF
Dioxane
9 (80)b
93
Dioxane
THF of 20% H2O
Dioxane of 20% H2O
THF
86
94
3
THF of 20% H2O
100
4
5
6
7
8
9
dioxane of 20% H2O
THF
Dioxane
THF of 20% H2O
Dioxane of 20% H2O
THF
97
65 (28)b
87
50 (36)b
82 (17)b
88
Dioxane
THF of 20% H2O
Dioxane of 20% H2O
THF
Dioxane
THF of 20% H2O
Dioxane of 20% H2O
78 (10)b
88
10
CH3
88
13 (67)b
67 (20)b
78
12 (70)b
9 (83)b
81
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
Dioxane
8
THF of 20% H2O
Dioxane of 20% H2O
THF
CH3O
Cl
88
87
0 (80)b
83
a
Isolated yield.
Yeild of recovered starting material.
b
Dioxane
THF of 20% H2O
Dioxane of 20% H2O
THF
89
98
10 (85)b
100
On the other hand, the reactivity of 2,2-dibenzyl 1,3-dichloro-
Dioxane
propanes was very low, and the corresponding cyclopropanes were
obtained in low yields (0–42%), together with the starting material,
depending on the solvents used. The best conditions were the re-
action in DMF solution of 20% H2O at 100 ꢀC for 7 days, as shown in
Table 3 (entry 6).
THF of 20% H2O
Dioxane of 20% H2O
THF
Dioxane
THF of 20% H2O
Dioxane of 20% H2O
95
91
10
17 (76)b
39 (61)b
99
8
98
Today, environmentally friendly organic synthesis has become
extremely popular, aiming toward green chemistry. Especially,
room temperature ionic liquids are attracting great interest as
a
Isolated yield.
Yield of recovered starting material.
b

Y. Tsuchiya et al. / Tetrahedron 65 (2009) 7533–7537
7535
Table 3
Table 5
Preparation of cyclopropanes from 1,3-dichlorpropanes with In powder
Reuse of ionic liquid for the cyclopropanation of 2,2-di(p-methoxybenzyl)-1,3-
dibromopropane
R
R
Cl
Cl
R
R
In (4.8 eq.)
R
R
Br
Br
R
R
In (2.4 eq.)
Solvent, 100 °C, 3 d
[bmim]BF4, 80 °C, 6 h
Entry
R–
Solvent
Yielda (%)
R =
CH3O
1
Dioxane
Dioxane of 20% DMF
DMF
DMF
DMF
DMF of 20% H2O
0 (100)b
7 (72)b
2c
3
2 (88)b
Reuse
Yielda (%)
4c
5c,d
6d
24 (49)b
31 (21)b
42 (42)b
0
1
2
3
4
5
88
85
85
87
83
91
a
Isolated yield.
b
c
Yield of recovered starting material.
NaI (2.0 equiv) was added.
Reaction time was 7 d.
d
a
Isolated yield.
environmentally friendly reaction media and reaction promotion
media for organic synthesis.23 These solvents possess interesting
and useful advantages, such as negligible vapor pressure, non-
flammability, high thermal stability at a wide range of temperatures,
and easy reusability.
Thus, we expected that ionic liquids would accelerate SET from In
powder to the substrate.24 First, we treated 2,2-di(p-methoxy-
benzyl)-1,3-diiodopropane with In powder (2.4 equiv) at 80 ꢀC in
many kinds of ionic liquids, such as [bmim]Br, [bmim]Cl, [bmim]BF4,
[emim]OTs, [bmpy]NTf2, and [bmim]PF6, and found that [bmim]Br,
[bmim]Cl, and [bmim]BF4 promoted the cyclopropanation effi-
ciently to give 1,1-di(p-methoxybenzyl)cyclopropane in high yields
(entries 1–6). Based on these results, 2,2-di(p-methoxybenzyl)-1,3-
dibromopropane was successfully cyclized to give the correspond-
ing 1,1-di(p-methoxybenzyl)cyclopropane in good yields in these
ionic liquids, respectively (entries 7–9). However, the same treat-
ment of 2,2-di(p-methoxybenzyl)-1,3-dichloropropane with In
powder gave the corresponding cyclopropane in moderate yields,
especially in [bmim]Br (entries 10–12). Here, ionic liquid [bmim]BF4
could be reused without any loss of chemical yield of the cyclopro-
pane. Thus, 2,2-di(p-methoxybenzyl)-1,3-dibromopropane was
treated with In powder (2.4 equiv) in [bmim]BF4 at 80 ꢀC. After ex-
traction of the cyclopropane from the reaction mixture with ether,
theionicliquid reaction mediacould be reused for thesame reaction,
consistently providing good yields untill the 5th time as shown in
R
R
X
X
R
R
In
R = aryl, alkyl
X = I, Br, Cl
-
e
Table 4
Preparation of cyclopropanes from 1,3-dihalopropanes with In powder in ionic
liquids
radical
3-exo-tet
R
R
R
R
X
X
In (2.4 eq.)
Ionic liquid, 80 °C, 6 h
R
R
X
A:
R =
B:
CH3O
R =
X
I
X
Entry
X
Ionic liquid
Yielda (%)
1
2
3
4
5
6
7
8
A
I
I
I
I
I
I
Br
Br
Br
Cl
Cl
Cl
I
I
I
I
I
[bmim]Br
[bmim]Cl
[bmim]BF4
[emim]OTs
84
84
92
X
71 (7)b
6 (94)b
46 (32)b
98
[bmpy]NTf2
[bmim]PF5
[bmim]Br
[bmim]Cl
[bmim]BF4
[bmim]Br
[bmim]Cl
[bmim]BF4
[bmim]Br
[bmim]Cl
[bmim]BF4
[emim]OTs
[bmpy]NTf2
[bmim]PF5
[bmim]Br
[bmim]Cl
[bmim]BF4
87
9
72 (14)b
48 (50)b
30 (42)b
31 (53)b
95
10c
11c
12c
13
14
15
16
17
18
19
20
21
R
R
-
R
R
e
B
98
97
92
X
X
THF-H2O or
dioxane-H2O
7 (84)b
26 (64)b
72
I
Br
Br
Br
R
CH3
81 (13)b
91
R
X
a
Isolated yield.
Yield of recovered starting material.
Reaction time was 48 h, and In (4.8 equiv) used.
not formed
b
c
Scheme 1. Plausible Reaction Mechanism.

7536
Y. Tsuchiya et al. / Tetrahedron 65 (2009) 7533–7537
Table 5. The same treatment of 2,2-dibenzyl-1,3-diiodopropane and
2,2-dibenzyl-1,3-dibromopropane with In powder in [bmim]Br,
[bmim]Cl, and [bmim]BF4 provided 1,1-dibenzylcyclopropane in
good yields, respectively (entries 13–15 and 19–21, Table 4).
As regards the reaction mechanism, when 2,2-disubstituted-1,3-
diiodopropanes were treated with In powder (2.4 equiv) in THF
solution of 20% H2O and dioxane solution of 20% H2O, only 1,1-di-
substituted cyclopropanes were obtained in high yields without the
formationof2,2-disubstituted1-iodopropanesand2,2-disubstituted
propanes, which could be formed through the reactions of the cor-
responding carbanions with H2O. This result suggests that the pres-
ent cyclization reaction of 2,2-disubstituted 1,3-dihalopropane with
In powder may proceed in the radical 3-exo-tet manner, as shown in
Scheme 1.
a vacuum pump for 1 h at 80 ꢀC. 1,3-Diiodopropane (0.4 mmol) and
In powder (0.96 mmol) were added to [bmim]BF4 (1 mL), and the
mixture was heated for 6 h at 80 ꢀC. Then, the reaction mixture was
extracted with ether (10 mLꢁ3). The solvent was removed to give
crude cyclopropane (purity ꢃ95%). If necessary, the residue was
purified by preparative TLC or column chromatography on silica gel
to provide pure corresponding cyclopropane.
4.4. General procedure for recyclic use of ionic liquids
with In powder
All reactions were carried out under an argon atmosphere. Be-
fore the reaction, the ionic liquid, [bmim]BF4 (1 mL) was dried with
a vaccum pump for 1 h at 80 ꢀC. 1,3-Dibromopropane (0.4 mmol)
and In powder (0.96 mmol) were added to [bmim]BF4 (1 mL), and
the mixture was heated for 6 h at 80 ꢀC. Then, the reaction mixture
was extracted with ether (10 mLꢁ3). Ether solvent was removed to
give crude cyclopropane (purity ꢃ95%). After removal of the solvent,
the residue was purified by preparative TLC or column chroma-
tography on silica gel to provide pure corresponding cyclopropane.
[Bmim]BF4 reaction media was reused as above, after drying by
vacuum pump for one hour at 80 ꢀC.
3. Conclusion
The In-mediated cyclopropanation of 2,2-disubstituted 1,3-
diiodopropanes and 1,3-dibromopropanes in dioxane solution of
20% H2O and THF solution of 20% H2O was successfully achieved in
moderately high yields. Extraction of the reaction mixture pro-
vided the products in high purity (purity ꢃ95%). However, the
cyclopropanation of 2,2-disubstituted-1,3-dichloropropanes did
not proceed efficiently. On the other hand, the cyclopropanation of
2,2-disubstituted-1,3-diiodopropanes and 2,2-disubstituted 1,3-
dibromopropanes with In powder in ionic liquids, such as
[bmim]Br, [bmim]Cl, and [bmim]BF4, at 80 ꢀC for 6 h proceeded
smoothly to provide the corresponding cyclopropanes in good
yields with high purity (purity ꢃ95%) without purification, al-
though the reactivity of 2,2-disubstituted 1,3-dichloropropane was
not sufficient to provide the corresponding cyclopropane in
moderate yield. The mechanism was proposed to involve the
radical 3-exo-tet cyclization based on Baldwin’s rule.
4.4.1. 1,1-Dibenzylcyclopropane
Oil; IR (neat) 3030, 2920, 1500, 1460, 1020, 760, 700 cmꢂ1 1H
;
NMR (400 MHz, CDCl3)
d
¼7.31–7.25 (4H, m), 7.24–7.16 (6H, m), 2.56
(4H, s), 0.52 (4H, s); 13C NMR (100 MHz, CDCl3)
d
¼140.1 (q), 129.5
(t), 128.0 (t), 126.0 (t), 41.5 (s), 20.8 (q), 10.7 (s); MS (FAB): m/z 222;
HRMS (EI) found: 222.1422 m/z, calcd for C17H18: Mþ¼222.1409.
4.4.2. 1,1-Di(p-methylbenzyl)cyclopropane
Oil; IR (neat) 3000, 2920, 1520, 1020, 810 cmꢂ1 1H NMR
;
(400 MHz, CDCl3)
s), 0.48 (4H, s); 13C NMR (100 MHz, CDCl3)
129.4 (t), 128.7 (t), 41.1 (s), 21.0 (p), 20.9 (q), 10.6 (s); MS (FAB):
d
¼7.08 (8H, d, J¼1.7 Hz), 2.51 (4H, s), 2.33 (6H,
d
¼137.0 (q), 135.3 (q),
4. Experimental section
4.1. General
m/z 250; HRMS (EI) found: 250.1734 m/z, calcd for C19H22
:
Mþ¼250.1722.
1H NMR and 13C NMR spectra were obtained with JEOL-JNM-
GSX-400, JEOL-JNM-LA-400, and JEOL-JNM-LA-500 spectrometers.
4.4.3. 1,1-Di(p-methoxybenzyl)cyclopropane
Oil; IR (neat) 2910, 2840, 1610, 1510, 1250, 1180, 1040, 820 cmꢂ1
;
Chemical shifts are expressed in ppm downfield from TMS in
d
units.
1H NMR (400 MHz, CDCl3)
d
¼7.09 (4H, d, J¼8.7 Hz), 6.83 (4H, d,
Mass spectra were recorded on JEOL-HX-110 and JEOL-JMS-ATII15
spectrometers. IR spectra were measured with a JASCO FT/IR-4100
spectrometer. Melting points were determined on a Yamato Melting
Point Apparatus Model MP-21. Silica Gel 60 (Kanto Kagaku Co.) was
used for column chromatography and Wakogel B-5F was used for
preparative TLC. In powder (Aldrich) was commercially available.
J¼8.7 Hz), 3.80 (6H, s), 2.49 (4H, s), 0.47 (4H, s); 13C NMR (100 MHz,
CDCl3)
d
¼157.8 (q), 132.2 (q), 130.3 (t), 113.5 (t), 55.2 (p), 40.6 (s),
21.1 (q), 10.5 (s); MS (FAB): m/z 283; HRMS (FAB) found: 282.1620
m/z, calcd for C19H22O2: MþH¼282.1620.
4.4.4. 1,1-Di(p-chlorobenzyl)cyclopropane
Oil; IR (neat) 2920, 1490, 1400, 1070, 1010, 800 cmꢂ1 1H NMR
;
4.2. General procedure for cyclopropanation of 1,3-
diiodopropanes with In powder in Aq solvents
(400 MHz, CDCl3)
d
¼7.24 (4H, d, J¼8.4 Hz), 7.07 (4H, d, J¼8.4 Hz),
2.48 (4H, s), 0.53 (4H, s); 13C NMR (100 MHz, CDCl3)
d
¼138.2 (s),
130.0 (s), 128.0 (s), 41.0 (s), 21.0 (s), 11.0 (s); MS (FAB): m/z 290;
HRMS (FAB) found: m/z, calcd for C17H16Cl2: MþH¼290.0629.
All reactions were carried out under an argon atmosphere. 1,3-
Diiodopropane (0.4 mmol) and In powder (0.96 mmol) were added
to a THF solution of 20% H2O (3 mL) in a reaction flask. The mixture
was refluxed for 24 h. Then, the reaction mixture was extracted
with ether (10 mLꢁ3). The ether extract was dried over Na2SO4 and
filtered. Then, the solvent was removed to give crude cyclopropane
(purity ꢃ95%). If necessary, the residue was purified by preparative
TLC or column chromatography on silica gel to provide pure cor-
responding cyclopropane.
4.4.5. 1,1-Di(dodecyl)cyclopropane
Oil; 1H NMR (400 MHz, CDCl3)
d
¼3.19 (4H, s), 1.43–1.10 (44H,
m), 0.88 (6H, t, J¼6.9 Hz); 13C NMR (100 MHz, CDCl3)
¼36.0 (s),
d
31.9 (s), 29.9 (s), 29.6 (s), 29.4 (s), 26.6 (s), 22.7 (s), 19.2 (q), 14.1 (p),
11.9 (s); MS (FAB): m/z 378; HRMS (EI) found: 378.4230 m/z, calcd
for C27H54: Mþ¼378.4226.
4.4.6. 1,1-Di-(10-undecenyl)cyclopropane
4.3. General procedure for cyclopropanation of 1,3-
diiodopropanes with In powder in ionic liquid
Oil; 1H NMR (400 MHz, CDCl3)
d
¼5.82 (2H, ddt, J¼17.2, 10.2,
6.8 Hz), 5.04–4.97 (2H, ddt, J¼17.2, 2.1, 1.7 Hz), 4.96–4.91 (2H, ddt,
J¼10.2, 2.1, 1.2 Hz), 2.05 (4H, m), 1.45–1.22 (28H, m), 1.18 (4H, dt,
All reactions were carried out under an argon atmosphere. Be-
fore the reaction, the ionic liquid, [bmim]BF4 (1 mL) was dried with
J¼7.5, 7.0 Hz), 0.15 (4H, s); 13C NMR (100 MHz, CDCl3)
¼139.2 (t),
d
114.0 (s), 43.1 (s), 34.7 (s), 31.8 (s), 29.67 (s), 29.61 (s), 29.59 (s), 25.6

Y. Tsuchiya et al. / Tetrahedron 65 (2009) 7533–7537
7537
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(s), 17.8 (t), 9.9 (s); MS (FAB): m/z 346; HRMS (FAB) found: 346.3617
m/z, calcd for C25H46: M¼346.3600.
Acknowledgements
Financial support in the form of a Grant-in–Aid for Scientific
Research (No. 20031007) from the Ministry of Education, Culture,
Sports, Science, and Technology, Japan is gratefully acknowledged.
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